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which can be termed renewable diesel and whose composition resembles that of petroleum-derived diesel
fuel (petro diesel), has been gaining attention in recent years. Several processes (cracking or pyrolysis, hydride
oxygenation) can be used to obtain fuels resembling petrodiesel (Takuya Ito et al, 2012). Figure 1 is a flow
chart for fuels from triacylglycerol containing feeds tocks from production to engine combustion.
Figure 1.Flowchart for transformation of lipid materials (biodiesel and renewable diesel by hydride oxygenation) to products
of engine combustion.
Biodiesel from animal fats compared with biodiesel from vegetable origin has the advantage a higher
cetane number, the most significant indicator of diesel combustion behavior (Tong et al., 2011); nevertheless,
the fuel produced from fats has higher cold filter plugging point because of this raw material has significant
content of saturated fatty acids (Lebedevas et al., 2006). Furthermore biodiesel from animal fats is less stable
for oxidation, this fact being attributed to the absence of natural antioxidants as compared to biodiesel of
vegetable origin (Sendzikiene et al., 2005). For these properties, the biodiesel produced from animal fats might
not be adequate to use it 100% pure in vehicles during cold weather; however might be used 100% pure in
boilers for heat generation. Alternatively, fats might be mixed with other raw materials to get a biodiesel obeying
such quality specifications, being even possible to enhance some biodiesel properties by incorporation of fats in
the raw material (Canoira et al., 2008; Dias et al., 2008).
In Iran, Fars province is one of the major meat producers. In 2012 its production corresponded to
nearly 108 thousand tons of poultry and 70 thousand tons of beef. Thus, meat-processing and rendering
industries produce annually a large amount of animal fats with different quality degrees. Part of this by-product
of high quality is generally destined for food, pharmaceutical and chemical industry. On the other hand, there
are often problems in management of fat residual fraction, leading to its inappropriate disposal. Also
pharmaceutical and chemical industries extract glycerol from animal fat and then throw out the other parts. So
animal fat as biodiesel production feedstock would be useful.
MATERIALS AND METHODS
In order to obtain waste animal fat for biodiesel production, the waste animal fat should be supplied
from slaughterhouse. Test samples were selected from slaughterhouse around shiraz (Shiraz is the capital city
of fars province, iran, at 2936 N latitude and N 5232 E longitude) with three different type .
Extraction and Purification of Fat from Animal Fats Samples
For drawing oil and removing moisture from the samples they were cooked in a large boiler (pot) at
about 110 C and the dried fat was used directly in the esterification reaction. Chemical composition of oils and
fats used in the biodiesel synthesis can influence processing and storage conditions, due to the percentage of
unsaturated fatty acids (Ramalho et al., 2011). Therefore, the Metcalf method was used to metilize the
extracted oil. Fatty acid profile was determined using a gas chromatography. Chromatogram of animal fat oil
used in this research work is shown in Figure 2.
85
High free fatty acid content of the oil caused transesterification reaction to fail and led to soap
production. For free fatty acid (FFA) content of more than 1%, the following equations (based on weight ratio)
were used for titration and calculation of catalyst rates(Gerpen et al., 2004):
% FFA
0 / 5 A N Wcat
W
KOH ( gr )
%FFA 0 /197 %1
(1)
(2)
0 / 86
Where:
A = Catalyst volume for oil titration (ml)
W = The sample value (g)
N = Normality
W cat= Molecular mass of catalyst (g) which is 56.1 for KOH
The free fatty acid (FFA) level of the animal fat was determined 11% using titration method, which is
not sufficient to complete the reaction with alkaline catalysts. The reduction of FFA esterification reaction was
carried out using methanol and sulfuric acid. After reactions proceeded to completion, the level of FFA was
reduced to less than 1%. The transesterification reaction started in the presence of methanol, alkaline catalyst
and the animal fat with free fatty acid levels of less than 1%.
Methanol (99.7%) and KOH (99%) used in this study, were provided from Merck company products. The most
preferred alcohol used in biodiesel production is methanol because of its low price, physical and chemical
advantages (polar and the shortest chain alcohol). It can easily react with triglycerides and catalysts (Alptekin
and Canakci, 2011). Potassium hydroxide (KOH, 99% assays) in the form of solid tablets was used as catalyst
as it shown in Figure 3:
86
Gas chromatography (GC) set, Perkin Elmer clarus-580 based on BS-EN 14103 standards and
equations (3 and 4) were used to determine biodiesel yield and percentage of methyl ester content in the
produced biodiesel. Therefore:
A A
IS
AIS
M IS
100
M
(3)
Where:
A= Total area under pick for fatty acids C6 to C14, V*sec.
AIS = Area under thr internal standard (methyl heptadecanoate) pick, V*sec.
MIS = Mass of applied internal standard (mg).
M = Mass of biodiesel sample (mg).
Conversion of percentage of oil to methyl ester (biodiesel) is obtained from following equation(4)
(Thanh et al., 2010):
FAME(%)=
w
3w
FAME
WCO
M
M
FAME
100
(4)
WCO
Where:
W FAME= Produced biodiesel (mg)
W WCO = Mass of animal fat (mg)
M FAME = Mean molecular mass for biodiesel
M WCO = Mean molecular mass for animal fat oil
For the transesterification to give maximum yield, the alcohol should be free of moisture and the FFA
content of the oil should be less than 0.5% (Geise, 2002). The absence of moisture in the transesterification
reaction is important because according to the following equation (shown for methyl esters),
R-COOCH3 + H2O R-COOH + CH3OH
(R = alkyl)
hydrolysis of the formed alkyl esters to FFA can occur. Similarly, because triacylglycerols are also
esters, the reaction of the triacylglycerols with water can form FFA. At 32C, transesterification was 99%
complete in 4 hours when using an alkaline catalyst (NaOH or NaOMe) (Gerpen and Knothe, 2005). Two
phases could be identified after the pre-treatment. The upper phase consisted of methanol, catalyst, H 2O,
resulted soap and impurities. This layer should be separated to reach acceptable levels for fuel parameters.
The lower phase mainly consisted of fats and the esterified fatty acids. For this purpose, the biodiesel was
obtained by transesterification reaction, via methylic routes. Samples and reaction final mixture were placed in
decantation funnels and allowed to stand overnight and centrifuged to ensure the complete phase separation
(methyl esters and glycerol). After reaction, the glycerol phase (bottom phase) was separated by decantation
and the biodiesel phase (upper phase) was heated at 85C (with anhydrous sodium sulfate, before filtration) to
eliminate methanol. The biodiesel was neutralized with KOH (20% KOH needed was to neutralize the added
H2SO4 as catalyst) and it was washed with distilled water to remove catalyst and reach neutral pH. The
collected fat was mixed with a basic solution of potassium hydroxide (KOH) to remove the free fatty acids (FFA)
in the form of soap. The soap was separated from the fat content by centrifugation. The purified fat was
processed to the next step, transesterification.
Transesterification of Fat
Animal fats were transesterified with acid catalyst and basic catalyst with and without pre-esterification.
Biodiesel of 89.0 wt.% ester content was obtained by acid-transesterification (9 wt.% H2SO4, 6:1 methanol:fats
molar ratio, 60 C, 48 h). Pre-esterification conditions were studied for different fats and acid catalysts: 0.5 wt.%
H2SO4 or 1.0 wt.% p-TsOH, 6:1 methanol:fats molar ratio, 65 C and 4 h made it possible to obtain fats with
acid value less than 0.5% FFA. Pre-treatment was effective for fats with different FFA content. Alkali
transesterification of esterified fats resulted in a product with 97.3 wt. % ester content. Biodiesel quality was
evaluated and most of its properties were well within EN 14214 standard (Encinar et al, 2011).
Transesterification of the purified fat described above was conducted to convert the triglycerides to
biodiesel. In this process, the recovered fat content was preheated to 100 C and cooled to room temperature
to remove the traces of water present. A solution of methanol and KOH (as a catalyst) were added to the fat.
The reaction mixture was refluxed at 60 C for 1 hour. Optimization of the transesterification reaction was
achieved by varying the amounts of methanol and potassium hydroxide. After the transesterification process,
the reaction mixture was allowed to cool to room temperature overnight. The glycerol layer, which contains unreacted alcohol and catalyst, was separated from the biodiesel. The top layer was then washed twice with
87
warm water (40-45 C) and with acidified water (0.5 wt% tannic acid) to remove the excess methanol and the
traces of catalyst (Kondamudi et al., 2009).
This two-step protocol typically gives high degrees of transesterification (>98%), with negligible
amounts of remaining unreacted (complete or partial) acylglycerols. The final ester product separates readily
from the polar liquid phase, which contains unreacted alcohol, the glycerol coproduct, and the catalyst.
The water washing step is intended to remove any remaining catalyst, soap, salts, methanol, or free
glycerol from the biodiesel Neutralization before washing reduces the amount of water required and minimizes
the potential for emulsions to form when the wash water is added to the biodiesel. After the wash process, any
remaining water is removed from the biodiesel by a vacuum flash process (Gerpen and Knothe, 2005).
After drying, the produced animal fat methyl esters (biodiesel) were characterized by determining their
viscosity, density, flash point and acid value and the purified biodiesel was characterized by Gas
chromatography (GC) set (Perkin Elmer clarus-580) based on BS-EN 14103 standards (Figure 4).
Figure 4.The Gas Chromatograph used for oil and produced biodiesel analysis.
A (%)
0.07%
2.64 %
26.50 %
0.19 %
29.60 %
32.01%
3.42 %
0.50 %
0.24 %
5.30%
0.25%
B (%)
0.09%
1.5%
27.90%
12.0%
20.00%
22.80%
10.50%
0.7%
0.01
----4.5%
C (%)
0.05%
2.33%
27.0%
3.50%
28.20%
26.50%
6.60%
0.7%
0.5%
2.80%
1.80%
88
They suggested that the methyl oleate formed may be hydrolyzed over a prolonged treatment and high
temperature; but these results correspond to high water content. In our study, water content is very low (Table
1) so its effect could only be expected in acidtransesterification reactions.
The major fatty acids of the feedstocks were palmitic (2628%) and oleic (3033%), acids with low
degree of unsaturation. Most properties of biodiesel depend on the used feedstock. It has been reported that
biodiesel viscosity and density can be predicted based on feedstock fatty acid profile. High viscosity is expected
because the main fatty acids have long chain of carbon and low degree of unsaturation, as well as no high
density is expected for the same reasons. Density increases with decreasing chain length and increasing
number of double bonds (Refaat, 2009). Also percent of FFA content of the samples was 11% on average.
Figure 5, shows the raw material before estrifacion condition:
Pre-esterification conditions
To obtain high ester content by pre-esterification, with H2SO4 as catalyst, followed by basictransesterification, with KOH as catalyst, the main variables of both steps were studied. Firstly pre-esterification
conditions were studied changing catalyst amount, methanol:fats molar ratio, and reaction temperature,
whereas the transesterification conditions were kept constant (1.5 wt.% KOH, 6:1 methanol:esterified fats molar
ratio, 65 C and 2 h of reaction time). This is a high catalyst amount to get the reaction of all tri-, di- and
monoglycerides from esterified fats to methyl esters if the raw material does not have an excessive acid value.
The effect of H2SO4 amount as catalyst in esterification reaction was studied. The decrease of the acid
value was high initially and then tended to stabilize. This behavior is according to previous research and the
lack of acid decrease at later times may be due to accumulation of water, because the sulfuric acid tends to
migrate into the water, out of the methanol, rendering it unavailable for the reaction (Diaz-Felix et al., 2009; Van
Gerpen et al., 2004).
Biodiesel specifications
The main parameters of a generic biodiesel obtained by pre-esterification followed by basictransesterification were determined. The obtained results and the specifications of European Standard EN
14214 are summarized in Table 2. Methyl ester content, density and viscosity met European Standard.
Although pure animal fats as feed stock usually have high viscosity, slightly out of the specification. This is due
to viscosity increase with the number of CH2groups in the FAME chain characteristic of the most saturated
animal fats (Canoira et al., 2008). However, the obtained biodiesel in this research is in the range of the
standard, close to upper limit.
Water content and flash point are in the ranges of the specifications.
Table 2.Biodiesel characterization
Parameter
Methyl ester content
Water content
Density 15 C
Density 40 C
Viscosity 40 C
Flash point
Standards
EN 14214
EN 14214
EN 14214
EN 14214
EN 14214
EN 14214
>96.5
<0.05
860-900
----3.50-5.00
>120
Biodiesel
98.0
0.05
874
875
4.95
169.2
Dimension
wt.%
wt.%
kg m-3
kg m-3
mm2s-1
C
CONCLUSION
Animal fats characterized by high free fatty acids were suitable feedstock to obtain biodiesel.By acidtransesterification a biodiesel with 89.0 wt.% ester content was produced. By esterification with 0.5 wt.%
89
H2SO4or 1.0 wt.% p-TsOH and 6:1 methanol:fats molar ratio an acid value less than 1.0% FFA was achieved
for fats with different FFA content, which were transesterified with only 0.5 wt.% KOH and 6:1 of methanol:fats
molar ratio, reaching 98 wt.% ester content in the biodiesel. The main biodiesel parameters were compared
with European Standard and most of the properties conformed with the standard specifications.
ACKNOWLEDGMENT
This research has been conducted using Bioenergy Research Centre facilities at Agriculture faculty of
TarbiatModares University. Hereby we would like to acknowledge cooperation and support of the research
center management and technicians throughout in this research.
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